Conjugated microporous polymer based on star-shaped triphenylamine-benzene structure with improved electrochemical performances as the organic cathode material of Li-ion battery
Conjugated microporous polymer based on star-shaped triphenylamine-benzene structure with improved electrochemical performances as the organic cathode material of Li-ion battery
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基于星形三苯胺-苯结构的共轭微孔聚合物作为锂离子电池有机正极材料具有改善的电化学性能
DOI：
10.1016/j.electacta.2018.08.047
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发表时间：
2018-10-01
影响因子：
6.6
通讯作者：
Zhang, Cheng
中科院分区：
文献类型：
--
作者：
Chen, Zhangxin;Li, Weijun;Zhang, Cheng
基于星形结构，设计合成了具有三个外围三苯胺单元的多个活性聚合位点的三苯胺衍生物1,3,5-三(4-二苯氨基苯基)苯(TTPAB)，并通过化学氧化聚合进一步制备成相应的共轭微孔聚合物PTTPAB。聚合物PTTPAB粉末表现出花球状形貌，具有高比表面积(595 m(2)/g)和丰富的平均直径为0.68 nm的微孔以及小直径约为2-5 nm的介孔。作为电池的有机正极材料，PTTPAB在50至500 mA g(-1)、2.5-4.2 Vat电流倍率范围内表现出比PTPAn(81、73、72、69、82 mAh g(-1))更优异的倍率性能，为84、82、81、80、84 mAh g(-1)。 PTTPAB 倍率性能的提高主要归因于共轭微孔聚合物结构和花状微球形态的丰富微孔和介孔导致的高比表面积。高表面积有利于Li+的可逆氧化还原反应并缩短Li+扩散路径，从而进一步降低电荷转移电阻（类似于PTTPAB的160Ω和PTPAn的920Ω），从而提高倍率性能。同时，PTTPAB在第50次充放电循环中表现出更稳定的循环寿命，几乎没有任何损失和更高的库仑效率。这些优异的电池性能和独特的微介孔结构使PTTPAB聚合物成为高倍率有机可充电电池有机正极材料的良好潜在候选者。 (C) 2018 Elsevier Ltd. 保留所有权利。
Based on the star-shaped structure, triphenylamine derivative 1,3,5-tris(4-diphenylamino-phenyl)benzene (TTPAB) with multiple active polymerization sites of three peripheral triphenylamine units was designed and synthesized, which was further prepared into the corresponding conjugated microporous polymer PTTPAB by chemical oxidative polymerization. The polymer PTTPAB powder exhibited the blossom sphere-like morphology with high surface area (595 m(2)/g) and plentiful micropores of the average diameter of 0.68 nm as well as mesopores of the small diameter of similar to 2-5 nm. Being explored as the organic cathode material of battery, PTTPAB exhibited more remarkable rate performance of 84, 82, 81, 80, 84 mAh g(-1) than that of PTPAn (81, 73, 72, 69, 82 mAh g(-1)) in the range of 2.5-4.2 Vat current rate from 50 to 500 mA g(-1) . This enhanced rate performances of PTTPAB was mainly attributed to the high specific surface area caused by the plentiful micropores and mesopores from the conjugated microporous polymer structure and blossom microspheres morphology. The high surface area can benefit to the reversible redox reaction available for Li+ and shorten Li+ diffusion pathway, that led to the more reduced charge transfer resistance (similar to 160 Omega for PTTPAB and similar to 920 Omega for PTPAn), thereby improving the rate performance. Meanwhile, PTTPAB showed more stable cycling life with hardly any loss and higher coulomb efficiency during the 50th charge/discharge cycle. These excellent cell performances and unique micro-mesopores structure make PTTPAB polymer a good potential candidate as the organic cathode materials for high rate performance organic reachargeable batteries. (C) 2018 Elsevier Ltd. All rights reserved.